Theoretical investigation of Mössbauer hyperfine interactions in ordered FeNi and disordered Fe–Ni alloys

Electronic structure spin-polarized calculations were performed for 79-atoms embedded clusters representing the ordered intermetallic compound FeNi, the fcc Fe-rich disordered alloy Fe₈₅Ni₁₅ in an antiferromagnetic (AFM) configuration, and the ferromagnetic (FM) disordered alloy Fe₅₀Ni₅₀. The spin-polarized discrete variational method (DVM) in Density Functional theory was employed. Spin magnetic moments, as well as the ⁵⁷Fe Mössbauer hyperfine parameters isomer shift and magnetic hyperfine fields, were obtained from the calculations. For FM Fe₅₀Ni₅₀, the effect of pressure on the hyperfine field and on the isomer shift was investigated, for three different local atomic configurations surrounding the ⁵⁷Fe probe atom. In the case of the isomer shift, the calculated values were compared to reported experimental data.     

Encapsulation of ZnS:Mn2+ nanocrystals with diblock copolymers

The encapsulation of the nanocrystalline manganese‐doped zinc sulfide (ZnS:Mn) in poly(styrene‐b‐2vinylpyridine) (PS‐PVP) diblock copolymers is reported. Below the critical micelle concentration in the absence of nanocrystals (NCs), inverse micelles of PS‐PVP were induced by adding ZnS:Mn NCs, the presence of which was confirmed by scanning force microscope and dynamic light scattering. In toluene, a PS‐selective solvent, the less‐soluble PVP blocks preferentially surround the ligand‐coated ZnS:Mn NCs. For PS‐PVP encapsulated ZnS:Mn NCs, the ratio of blue emission to orange emission of ZnS:Mn NCs is dependent on both the concentration of PS‐PVP and the solvent quality. The pyridine of PVP blocks form complexes with the Zn atoms via the nitrogen lone pair and thus the sulfur vacancies are passivated. As a result, the defect‐related blue emission is selectively quenched even when the micelles are not formed. As the concentration of PS‐PVP encapsulating the ZnS:Mn NCs increases, the intensity of blue emission decreases. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3227–3233, 2006     

Thermal characterization of social vespid silk

In this paper we try to establish a link between the microclimate in the wasp nest and the structure and thermal stability of vespid silk. We suggest that there are at least two types of water that is absorbed by the silk of Oriental hornets, namely, surface water and intrinsic structural water. The release of both types of water was found to be reversible. The enthalpy values of the endothermic peaks associated with the release of water from different silk samples do not differ substantially and are in the range of 106 to 130 J g^-1 for the Vespa orientalis male larvae silk (sample #1), Paravespula germanica (yellowjacket) worker larvae silk (#3) and Vespa orientalis nest envelope(#4). For the Vespa orientalis worker larvae silk (sample #2), however, it is twice as large (228 J g^-1). This is in agreement with the increased total amount of absorbed water. The silk studied has a fibrilar structure with interconnecting surfaces overlying entire regions. It is assumed that the initial water loss stems from water evaporation from the coat of the fibers - a daily occurrence in the hornets' nest. Heating to above 70°C may result in structural changes in the silk core. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effects of processing on the structure of zein/oleic Acid films investigated by x-ray diffraction

Zein films plasticized with oleic acid were formed by solution casting, by the stretching of moldable resins, and by blown film extrusion. The effects of the forming process on film structure were investigated by X-ray diffraction. Wide-angle X-ray scattering (WAXS) patterns showed d-spacings at 4.5 and 10 A, which were attributed to the zein alpha-helix backbone and inter-helix packing, respectively. The 4.5 A d-spacing remained stable under processing while the 10 A d-spacing varied with processing treatment. Small-angle X-ray scattering (SAXS) detected a long-range periodicity for the formed films but not for unprocessed zein, which suggests that the forming process-promoted film structure development is possibly aided by oleic acid. The SAXS d-spacing varied among the samples (130-238 A) according to zein origin and film-forming method. X-ray scattering data suggest that the zein molecular structure resists processing but the zein supramolecular arrangements in the formed films are dependent on processing methods. Structural model for a zein molecular aggregate (based on Matsushima et al.10). Rectangular prisms of individual zein molecules are hexagonally aligned parallel to each other.     

Expedient synthesis of substituted imidazoles from nitriles

Expedient and practical new methodology for the synthesis of substituted imidazoles was developed to provide a rapid access to a variety of 2-substituted, 1,2-disubstituted and 1,2,4-trisubstituted imidazoles by the direct CuCl-mediated reaction of nitriles with α-amino acetals in an intermolecular as well as intramolecular fashion.     

Mechanism of the glutathione transferase-catalyzed conversion of antitumor 2-crotonyloxymethyl-2-cycloalkenones to GSH adducts

Human glutathione (GSH) transferase (hGSTP1-1) processes with similar kinetic efficiencies the antitumor agents 2-crotonyloxymethyl-2-cyclohexenone (COMC-6), 2-crotonyloxymethyl-2-cycloheptenone (COMC-7), and 2-crotonyloxymethyl-2-cyclopentenone (COMC-5) to 2-glutathionylmethyl-2-cyclohexenone, 2-glutathionylmethyl-3-glutathionyl-2-cycloheptenone, and 2-glutathionylmethyl-2-cyclopentenone, respectively. This process likely involves initial enzyme-catalyzed Michael addition of GSH to the COMC derivative to give a glutathionylated enol(ate), which undergoes nonstereospecific ketonization, either while bound to the active site or free in solution, to a glutathionylated exocyclic enone. Free in solution, GSH reacts at the exomethylene carbon of the exocyclic enone, displacing the first GSH to give the final product. This mechanism is supported by the observation of multiphasic kinetics in the presence of high concentrations of hGSTP1-1 and the ability to trap kinetically competent exocyclic enones in aqueous acid using COMC-6 and COMC-7 as substrates. That the exocyclic enone is formed by nonstereospecific ketonization of an enol(ate) species is indicated by the observation that COMC-6 (chirally labeled with deuterium at the exomethylene carbon) gives stereorandomly labeled exocyclic enone. The isozymes hGSTP1-1, hGSTA1-1, hGSTA4-4, and hGSTM2-2 catalyze the conversion of COMC-6 to final product with similar efficiencies (K(m) = 0.08-0.34 mM, k(cat) = 1.5-6.1 s(-)(1)); no activity was detected with the rat rGSTT2-2 isozyme. Molecular docking studies indicate that in hGSTP1-1, the hydroxyl group of Tyr108 might serve as a general acid catalyst during substrate turnover. The possible significance of these observations with respect to the metabolism of COMC derivatives in multidrug resistant tumors is discussed.     

Characterization of CNS disorders and evaluation of therapy using structural and functional MRI

Modern drug development requires technologies that allow rapid translation from the preclinical to the clinical stage. It is obvious that non-invasive imaging modalities such as magnetic resonance imaging (MRI) will play a central role in this regard. This article reviews the use of structural and functional MRI readouts for characterization of central nervous system (CNS) disorders and evaluation of the efficacy of potential CNS drugs. Examples comprise dementia of Alzheimer's type, cerebral ischemia, and neuroinflammation covering both clinical and preclinical aspects. In these examples MRI has been used to obtain relevant structural information on brain atrophy, on the location and extent of ischemic brain areas, and on the number and distribution of demyelinated plaques. These structural data are complemented by readouts assessing the functional consequences associated with the pathomorphological changes. In the last decade, MRI has evolved into a standard tool for the development of CNS drugs. With regard to target-specific/molecular imaging applications MRI is limited by its inherently low sensitivity; complementary imaging modalities utilizing optical and radionuclear reporter systems will thus be required.     

Polyfluorothiolate derivatives of rhodium(I). Crystal and molecular structure of [Rh(μ-SC6HF4)(C8H12)]2

Summary The thiolato-bridged dinuclear compounds [Rh(-SR)-(COD)]₂, where R=p-C₆HF₄ (1),p-C₆H₄F (2) and CF₃ (3), are obtained from the chloro-bridged analogue by ligand exchange.Compound (1) crystallizes in the space group P₁ with a=9.740(3)Å, b=11.642(4)Å, c=13.997(6)Å, =103.87(3)°, =106.98(3)° and =105.10(2)°; z=2. In this dinuclear molecule both Rh atoms have a square planar coordination sharing one edge, namely the two sulphur bridging atoms. The Rh—Rh separation of 2.96 Å is consistent with at most a very weak metal-metal interaction. Upon addition of CO the dimeric [Rh(-SR)(CO)₂]₂ (4), (5) and (6) are obtained, but addition of PPh₃ affords the monomeric species [Rh(SR)(PPh₃)-(COD)] (7), (8) and (9). Reactions of the dimeric tetracarbonyl derivatives with PPh₃ vary with the nature of R; [Rh(-SR)(PPh₃)(CO)]₂ is obtained when R=p-C₆H₄F (10) and CF₃ (11) but monomeric [Rh(SR)-(PPh₃)(CO)₂] (12) is produced when R=p-C₆HF₄. The latter mononuclear compounds, with R=p-C₆H₄F (13) and CF₃ (14), are also formed by reaction of [Rh(SR)-(PPh₃)(COD)] with CO.     

Trace and major elements in serum of patients with chronic myelogenous leukemia

Summary Major and trace elements were determined in serum of patients with chronic myelogenous leukemia (CML) using total reflection X-ray fluorescence induced by synchrotron radiation (SRTXRF). CML affects 1 to 2 people per 100,000 and accounts for 7-20% cases of leukemia. It was possible to determine the concentrations of the following elements: P, S, Cl, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Br and Rb. Using analysis of variance (ANOVA) it was observed that the contents of the P, S, Ca, Cr, Mn, Fe, Cu and Rb elements differed significantly at a = 0.05 between groups of healthy subjects and CML patients and also genders (males and females).     

Methyl scanning: total synthesis of demethylasterriquinone B1 and derivatives for identification of sites of interaction with and isolation of its receptor(s)

The principle of methyl scanning is proposed for determination of the sites of interaction between biologically active small molecules and their macromolecular target(s). It involves the systematic preparation of a family of methylated derivatives of a compound and their biological testing. As a functional assay, the method can identify the regions of a molecule that are important (and unimportant) for biological activity against even unknown targets, and thus provides an excellent complement to structural biology. Methyl scanning was applied to demethylasterriquinone B1, a small-molecule mimetic of insulin. A new, optimal total synthesis of this natural product was developed that enables the family of methyl scan derivatives to be concisely prepared for evaluation in a cellular assay. The results of this experiment were used to design a biotin-demethylasterriquinone conjugate for use as an affinity reagent. This compound was prepared in tens of milligram quantities in a four-step synthesis.